Preparation of trisazo dyes



Patent ed- June 4, 1929.

UNITED STATES HENRY JORDAN, OF WILMINGTON, DELAWARE, ASSIGNOR 'I'O E. I. DU PONT DE PATENT. OFFICE.

NEMOURS & COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF D-ELA- WARE.

No Drawing.

This invention relates to the preparation of trisazo dyes for direct application to cotton. More particularly it is concerned with gray to blue-green and green trisazo dyes made from a derivative of an amino-azo-compound and a 1 S-aminonaphthol derivative. In brief the process consists in coupling a diazo compound to an amine or an amino-sulphonic acid, diazotizing the obtained monoazo dye, coupling it to a 1: 8-amino-naphthol derivative, diazotizing the vdisazo dye again and finally coupling the resulting intermediate to a compound having either the grouping CHCO as, for example, aceto-acetanilide or other aceto-acetarylids or their homo- ,logues and derivatives and derivatives of pyrazolone or having the grouping C= CH,

as for example in methyl-ketole.

The process can best be disclosed by the presentation of a number of examples of actual embodiments thereof. It is to be understood, however, that such examples are furnished by way of illustration only, and'that the details of procedure followed therein as well as the proportions, reagents, temperatures, etc.,. therein disclosed are susceptible to variation and substitution.

3 E trample 1.

107 parts of ortho-toluidine are diazotized in the usual way with 69 parts of sodium nitrite. The diazo solution is added-to a solution of 223 parts of l zfi-Cleves acid in 4000 parts of water and 53 parts of sodium carbono-toluidine,

1 4-naphthylene-diamine-6-sulphonic acid,

.diazotization stir for one hour.

rnnPAnATIon or TRISAZO, DYEs.

Application m October 22, 1925. Serial No. 64,254.

ate, containing 170 parts of sodium "acetate. The coupllng is made at 1015 After one hours st1rr1ng itwill be complete. It is made slightly alkaline with sodium hydroxide, then acldified again with 450 parts of a 31% hydrochloric acid solution. 69 parts of sodium nitrite are added at 1015 0., leaving the The diazo compound thus obtained is added to a solution of 341 parts of 1:8-amino-naphthol-3:6-disulphonic acid containing 700 parts of sodium carbonate. The temperature of the coupling should be 510 C. The color of this intermediate dye is bright greenish-blue. The dye is precipitated with salt and filtered. The paste is stirred up'with 5000 parts of Water, acidified with 400 parts of a 31% hydrochloric acid, and 69 partsof sodium nitrite are added. Meanwhile the temperature of the mixture is kept at about 25 C. The blue color of the dye changes to the dark green of diazo compound. After hours stirring the diazo compound is added to a solution of 177 parts of aceto-acetanilide in 4000 parts of Water and 40 parts of sodium hydroxide, which contains 550 partsof sodiumcarbonate. The temperature during the coupling is 510 C.. The dye is salted out at about 7 0 C. In its dry form it is a darkbronzy looking powder, which dissolves in water with a bright green color, dyeing cotton ingreen shades of a remarkable fast'ness to light. It has probably the following'structural formula:

soma- 1 :7 diam'ino-8-hydroxy-naphthalene3 6- disulphonic acid, alpha-amino-aceto-acetanilide.

Using an equivalent amount of phenylmethyl-pyrazolone instead of aceto-acetanidye. It has probably-the following structulide, a yellower', duller green is obtained of ral formula:

. similar properties as the aceto-acetanilide I C H3 l soars Example 2.

Substituting, for the 107 parts of o-toluidine employed in Example-1, 173 parts of para-sulphanilic acid, a somewhat bluer, but much brighter green is obtained, the fastness hi light being the same as that from Exame 1. v p The pyrazolone dye again shows a yellower,

duller shade than the aceto-acetanilide dye.

The reduction products resulting from reducing with stannous chloride are the same Y CaNa The reduction products resulting from reduction with stannous chloride are the same S OaNa as in Example 1, except 1 4-naphthionic acid v is obtained instead of o-toluidine.

Example Using 127.5 parts of orthochloroaniline, instead of 107 parts of o-toluidine, as in Example 1', and 223 parts of 1:7 -Cleves acid instead of 1 6-Cleves acid, a dye is obtained which dissolves in water with a dark bluishgreen color and dyes cotton. in greenish-gray 4-0 shades.

S O Na SOaNB .jlhe reduction "products are the same as l in Example 1, except alpha-naphthylamine is obtained instead of o-to'luidine.

Example 6. p 303 parts of 2-naphthylamine-4: 8-disulphonic acid are diazotized in-the usual way with 69 parts of sodium nitrite. 143 parts of alpha-naphthylamine, dissolved at 80 C. 1n

' 2000 parts of water and .140 parts of a 31% hydrochloric acid, are added to the diazo compound, keeping the coupling temperature co e some as in Example 1, except sulphanilic acid is obtained instead of o-toluidine.

' Example 3.

Using instead of 107 parts of o-toluidine, as in Example 1, 223 parts of 1 l-naphthionic acid, leaving the other intermediates and conditions the same, a little yellower and even brighter green than that one of Example 2 is obtained. It has probably vthe following structural formula:

On reducing with stannous chloride,this

dye willgive the same compounds as that of Example 1, except orthochlor'oaniline is obtained instead of o-toluidine.

, Example 5.

Using 1&3 parts of alpha-naphthylamine ample 1, leaving the other intermediates and conditions'the same, an olive dye is obtained, soluble in water with a yellowish-green color,

dyeing cotton in deep olive shades. It has probably the following structural formula SOsNa at 10l5 C. The mineralacid reaction is neutralized by sodium acetate. The coupling will be complete after about one hours stirinstead of 107 parts of o-toluidine as in Exa solution of 341 part s of 1:8-amino-naphthol-3 6-disulphonic acid containing 700 parts of sodium carbonate, keeping the coupling temperature at 5-10" C. The dye is precipitated with salt and filtered. The last diazotizationand coupling to aceto-acetanilide .is carried out as described in Example 1. The dye dissolves in water with a bright green color, dyeing cotton in green shades, which are a trace duller than those of Example 3.

On reducing with stannous chloride the following compounds will be obtained:

2-naphthylamine- 4 S-disulphonic acid,

1 t-naphthylene-diamine,

1 7 diamino-8-hydroxy-naphthalen-e-3 6- disulphonic acid, alpha-amino-aceto-acetanilide.

Example 7. 223 parts of 1 5-napl1tl1ylamine-sulphonic phonic acid, and I 1-phenyl-3-methyl-4-amino-pyrazolone Example 8.

341 parts of 1:8am1no-naphthol-3:6-disulphonic acid are diazotized in the usual way. To the diazo compound there is added a solution of 143 parts of alpha-naphthylamine in 2000 parts of water and 1&0 parts of hydrochloric acid (31%) keeping the temperature ofthe coupling at about 10 C. The acidity is neutralized with sodium acetate. The coupling will be complete after onehalf hours stirring. The coupling is made slightly alkaline with sodium hydroiide, cooled to 0, acidified again with. 450 parts of hydrochloric acid and diazotized with 69 parts of sodium nitrite. The diazo compound is-stirred one-half hour and is then coupled to 3 11 parts of 1:8-amino-naphthol-3z6-di- N=N8N=N SOaNa p SOaNa -''bined with 239 parts of 1 S-amino-naphthold-sulphonic acid, dissolved in 3000 parts of Water and 700 parts of sodium carbonate. The disazo dye is precipitated with salt and filtered. It is rediazotized in the same way as shown in Example 1. The diazo compound is coupled. at 5-10 C. to a solution of 1743 parts of phenyl-methyl-pyrazolone in 1000 parts of waterand 550 parts of sodiurn carbonate. The dye is precipitated with salt and filtered. It dissolves in Water with a yellowish-olive color, dyeing cotton in yel loWish-olive shades. It has probably the following structural formula:

sulphonic acid dissolved in-3000 parts of water and 700 parts of sodium carbonate. The dye is precipitated with salt and filtered. The last diazotization and coupling to acetoacetanilide is carried out in the same way as shown in Example 1. This dye is soluble in water with a bright greenish-blue color, dyeingcottom in bright greenish-blue shades.

On reducing with stannous chloride, the following compounds will be obtained; I

1 8-amino-naphthol-3 6-disulphonic acid, 1 7-diamin-o-8-l1ydroxy naphthalene-3 6- disulphonic acid, I

1:4 -naphthylenediamine, and alpha-amp no-aceto-acetanilide.

EwampZeQ.

Using instead of 17 7 .parts of aceto-acetani lid as in'Example 3, 131 parts of methylketole,

which is dissolved in 350-parts of 31% hydrochlorie acid, then added to the last intermediate diazo solution, making the couplin alkaline with soda ash thereafter, leaving all other conditions the same as in Examp'le 3, a dye is obtained, which is soluble in water 1 with a dark green color, and dyes cotton in dye of Example It has probably the folsomewhat yellower duller shades than the lowing structural formula:

OaNa

The reduction products by stannous chloride are the same as in Example 3, except instead of alpha-amino-aceto-acetanilid there is obtained amino methylketole.

SOaNa E mample I Substituting in Example 3 for 177 parts of 15 I aceto-acetanilid 227 parts of aceto-acet-alphanaphtha-lid (made by condensation of acetoaceti'c-ester with alpha naphthylamine) leaving all other conditions the same as in Example 3, a somewhat yellower, slightly duller green is obtained. It has 'probably'the following structural formula;

C-GHa SOaNa SOaNa SOJNB methods from either a neutral or slightly alkaline dye-bath. They may also be used on silk with a slightlyacid,'for example acetic acid, dye bath. It Will be noted that in every instance the compound employed for the last component comprises this group wherein R represents a radical containing either a'CO -CH= group or .a C=H group.

' lected from the group including acyl-acetarylids, aryl pyrazolones and alkyl ketoles.

2. The process of producing a trisazo dye which comprises diazotizing a disazo compound prepared by coupling an aromatic '60 diazo-azo compound to a 1:8-amino naphthol compound having a free amino group at tached to the nucleus and coupling the resulting diazo compound to a compound selectedfrom the group including aceto-acetarylids, 5 aryl pyrazolones and methyl ketoles.

3. The process of producing a trisazo dye which comprises diazotizing a disazo com pound prepared by coupling an aromatic diazo-mono-azo compound to a 1:8-amino naphthol sulfonic acid having a free amino group attached to the nucleus and coupling the resulting diazo-disazo compound to. an aceto-acetarylid.

4. The process of producing a tr'isazo dye which comprises diazotizing a disazo compound prepared by coupling anaromatic diazo-mono-azo compound to a 1:8-amino naphthol compound having a free amino group attached to the nucleus and coupling 80.

the resulting diazo-disaz o compound to an aceto-acetani-lid.

5. The process of preparing a trisazo dye comprising diazotizing an aryl amino compound, coupling the diazo compound to an aromatic amino compound to obtain an azo compound, diazotizing said compound, coupling the resulting diazo compound to a 1 8- amino naphthol sulfonic acid having a free amino group attached to the nucleus, diazotizing again and coupling the diazo com pound with a compound having the grouping l CH,COCHCONHR, wherein R represents a radical containing an aryl group.

6. The process of preparing a trisazo dye comprising diazotizing ortho-toluidine, coupling the diazo compound to an aromatic amino compound to obtain a mono-azo compound, diazotizing said compound, coupling the resulting diazo compound to 1:8aminonaphthol-3 6-disulfonic acid to obtain a disazo compound, diazot-izing again and coupling the diazo compound with aceto-acetanilid.

7. A trisazo (lye comprising the grouping 1 8-azo naphthol coupled to an end component selected from the group including acyl acetarylids, aryl pyrazolones and alkyl' ketoles.

8. A trisazo dye comprising the grouping 1:8-azo naphthol coupled to an end component selected from the group including acetoacetarylids, aryl pyrazolones and methyl ketoles.

9. A trisazo dye obtainable by coupling a diaZo-disazo compound, derived from compounds of the benzene or naphthalene series and containing a 1 8-amino-naphtho1 sultonic acid group in coupling position, with a compound selected from the group including accto-acetarylids, aryl pyrazolones and methyl ketoles.

10. A trisazo dye obtainable by coupling a diaZo-disazo compound, derived from compounds of the benzene or naphthalene series and containing a 1:8-amino-naphthol sult'onic acid group in coupling position, with aceto-acetanilid.

11. A trisazo dye comprising the group 1:8azo-naphtli0l coupled to an end component having the grouping HENRY JORDAN.

Certificate of Correction.

Patent No. 1,716,063.

Granted June 4', 1929, to

HENRY JORDAN.

a It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: 7 Page 1, line 55, after the word of second occurrence, insert the article the;

page 2, in the formula after line 27, under the first doublering, for SC Na read SO Na; page 3, line 80, for the misspelled word cottom read cotton; page 4, strike out line 45 and insert instead. either a 0O-0 the said Letters Patent should be read with these H: group or a %OH; and that corrections therein that the same may conform to the record .of the casein the Patent Oflice.

Signed and sealed this 2nd day of July, A. D. 1929.

g [SEAL] M. J. MOORE, 4 Acting Oommiss'ioner'of Patent:;.

Certificate of Correction.

Patent No. 1,716,063. Granted June 4, 1929, to HENRY JORDAN.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Page 1, line 55, after the Word of second occurrence, insert the article the; page 2, in the formula after line 27, under the first double ring, for SC Na read SO Na; page 3, line 80, for the misspelled Word cottom read cotton; page 4, strike out line 45 and insert instead either a 0OOH= group or a' O OH; and that the said Letters Patent should be read With these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 2nd day of July, A. D. 1929.

M. J. MOORE,

[SEAL] Acting Commissioner of Patents. 

